Naphthalene anhydride

Photolytic. Based on data for structurally similar compounds, acenaphthylene may undergo photolysis to yield quinones (U.S. EPA, 1985). In a toluene solution, irradiation of acenaphthylene at various temperatures and concentrations all resulted in the formation of dimers. In water, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, 1,2-epoxyacenaphthylene, and 1-naphthoic acid. In methanol, ozonation products included 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, methyl 8-formyl-1-naphthoate, and dimethoxyacetal 1,8-naphthalene dialdehyde (Chen et al., 1979). Acenaphthylene reacts with photochemically produced OH radicals and ozone in the atmosphere. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with OH radicals (500,000/cm ) at 25 °C are 8.44 x lO " cmVmolecule-sec and 5 h, respectively. The rate constants and corresponding half-life for the vapor-phase reaction of acenaphthylene with ozone at 25 °C are... 

Chemical/Physical. Ozonation in water at 60 °C produced 1,8-naphthalene dialdehyde, 1,8-naphthalene anhydride, 1,2-epoxyacenaphthylene, 1-naphthoic acid, and 1,8-naphthaldehydic acid (Calvert and Pitts, 1966). 

Naphthalenic anhydride, lamelliconic anhydride (77), its carbonate (78), and several related compounds were isolated from Verticillium lamellicola (McCorkindale et al., 1983). FR-901235 (79), a new immunomodulator produced by Paecilomyces cameus [<-4882 (Shibata et al., 1989), has a similar chemical structure to lamelliconic anhydride. 

Example 13.1 Phthalic anhydride is an important intermediate for the plastics industry. Manufacture is by the controlled oxidation of o-xylene or naphthalene. The most common route uses o-xylene via the reaction... 

Most naphthalene produced is utilized in the manufacture of phthalic anhydride, for plasticizers, alkyd resins and polyesters. It is also used in the manufacture of 2-naphlhol and insecticides. Naphthalene derivatives are of importance, particularly as dyestufT intermediates. 

A further example is given below illustrating the use of a dibasic anhydride (succinic anhydride) the succinoylation reaction is a valuable one since it leads to aroyl carboxylic acids and ultimately to polynuclear hydrocarbons. This general scheme of synthesis of substituted hydrocarbons through the use of succinic anhydride is sometimes called the Haworth reaction. Thus a-tetralone (see below) may be reduced by the Clemmensen method to tetralin (tetrahydronaphthalene) and the latter converted into naphthalene either catal3d.ically or by means of sulphur or selenium (compare Section, VI,33). 

Acetoxylation and nitration. It has already been mentioned that 0- and m-xylene are acetoxylated as well as nitrated by solutions of acetyl nitrate in acetic anhydride. This occurs with some other homologues of benzene, and with methyl phenethyl ether,ii but not with anisole, mesitylene or naphthalene. Results are given in table 5.4. 

Davies and Warren" found that when 1,4-dimethylnaphthalene was treated with nitric acid in acetic anhydride, and the mixture was quenched after 34 hr, a pale yellow solid with an ultraviolet spectrum similar to that of a-nitro-naphthalene was produced. However, if the mixture was allowed to stand for 5 days, the product was i-methyl-4 nitromethylnaphthalene, in agreement with earlier findings. Davies and Warren suggested that the intermediate was 1,4-dimethyl-5 nitronaphthalene, which underwent acid catalysed rearrangement to the final product. Robinson pointed out that this is improbable, and suggested an alternative structure (iv) for the intermediate, together with a scheme for its formation from an adduct (ill) (analogous to l above) and its subsequent decomposition to the observed product. 

Davies and Warren have investigated the nitration of naphthalene, ace-naphthene and eight dimethylnaphthalenes in acetic anhydride at o °C. Rates relative to naphthalene were determined by the competition method, and the nitro-isomers formed were separated by chromatographic and identified by spectrophotometric means. The results, which are summarised in the table, were discussed in terms of various steric effects, and the applicability of the additivity rule was examined. For the latter purpose use was made of the data of Alcorn and Wells (table 10.2) relating to the nitration of monomethyl-naphthalenes at 25 °C. The additivity rule was found to have only limited utility, and it was suggested that the discrepancies might be due in part to the... 

Naphthalimides are prepared from naphthaUc anhydride obtained from naphthalene-1,8-dicarboxyhc acid, ie, the oxidation product of acenaphthene or its derivatives, by reaction with amines. They are utilized for synthetic fibers such as polyesters. 

Isopropylnaphthalenes produced by alkylation of naphthalene with propjdene have gained commercial importance as chemical intermediates, eg, 2-isopropylnaphthalene [2027-17-OJ, and as multipurpose solvents, eg, mixed isopropylnaphthalenes. Alkylation of naphthalene with alkyl haUdes (except methyl hahdes), acid chlorides, and acid anhydrides proceeds in the presence of anhydrous aluminum chloride by Friedel-Crafts reactions (qv). The products are alkylnaphthalenes or alkyl naphthyl ketones, respectively (see Alkylation). 

Oxidation. Naphthalene may be oxidized direcdy to 1-naphthalenol (1-naphthol [90-15-3]) and 1,4-naphthoquinone, but yields are not good. Further oxidation beyond 1,4-naphthoquinone [130-15-4] results in the formation of ortho- h. h5 ic acid [88-99-3], which can be dehydrated to form phthaUc anhydride [85-44-9]. The vapor-phase reaction of naphthalene over a catalyst based on vanadium pentoxide is the commercial route used throughout the world. In the United States, the one phthaUc anhydride plant currently operating on naphthalene feedstock utilizes a fixed catalyst bed. The fiuid-bed process plants have all been shut down, and the preferred route used in the world is the fixed-bed process. 

The naphthalene is vaporized, mixed with air, and fed to the top of the reactor. This process also allows for mixtures of ortho- s.yXen.e [95-47-6] to be mixed with the naphthalene and air, which permits the use of dual feedstocks. Both feedstocks are oxidized to phthaUc anhydride. The typical range of reactor temperature is 340—380°C. The reactor temperatures are controlled by an external molten salt. 

The quahty of naphthalene required for phthaUc anhydride manufacture is generally 95% minimum purity. The fixed plants do not require the high (>98%) purity naphthalene product and low (<50 ppm) sulfur. The typical commercial coal-tar naphthalene having a purity ca 95% (freezing point, 77.5°C), a sulfur content of ca 0.5%, and other miscellaneous impurities, is acceptable feedstock for the fixed-bed catalyst process based on naphthalene. 

The decline in naphthalene production in 1973 primarily resulted from competition with o-xylene as the feedstock for phthaHc anhydride. Periods of feedstock shortages and the loss of one principal producer also affected petroleum naphthalene output. 

The higher price of the petroleum product results from its higher quaUty, ie, higher purity, lower sulfur content, etc. The price of cmde coal-tar naphthalene is primarily associated with that of o-xylene, its chief competitor as phthaUc anhydride feedstock. 

The U.S. naphthalene consumption by markets for 1992 is Hsted in Table 9. The production of phthaHc anhydride by vapor-phase catalytic oxidation has been the main use for naphthalene. Although its use has declined in favor of o-xylene, naphthalene is expected to maintain its present share of this market, ie, ca 18%. Both petroleum naphthalene and coal-tar naphthalene can be used for phthaHc anhydride manufacture. U.S. phthaHc anhydride capacity was 465 X lOM in 1992 (38). 

Methyl- and dimethylnaphthalenes are contained in coke-oven tar and in certain petroleum fractions in significant amounts. A typical high temperature coke-oven coal tar, for example, contains ca 3 wt % of combined methyl- and dimethylnaphthalenes (6). In the United States, separation of individual isomers is seldom attempted instead a methylnaphtha1 ene-rich fraction is produced for commercial purposes. Such mixtures are used for solvents for pesticides, sulfur, and various aromatic compounds. They also can be used as low freezing, stable heat-transfer fluids. Mixtures that are rich in monomethyinaphthalene content have been used as dye carriers (qv) for color intensification in the dyeing of synthetic fibers, eg, polyester. They also are used as the feedstock to make naphthalene in dealkylation processes. PhthaUc anhydride also can be made from m ethyl n aph th al en e mixtures by an oxidation process that is similar to that used for naphthalene. 

The first of the benzene polycarboxyUc acids to become a commercial product was phthabc acid, mosdy in the form of the anhydride. The anhydride is obtained by the catalytic vapor-phase air oxidation of o-xylene or naphthalene. The lUPAC name of phthabc anhydride is 1,3-isobenzofurandione... 

Manufacture and Processing. Until World War II, phthaUc acid and, later, phthaUc anhydride, were manufactured primarily by Hquid-phase oxidation of suitable feedstocks. The favored method was BASF s oxidation of naphthalene [91-20-3] by sulfuric acid ia the presence of mercury salts to form the anhydride. This process was patented ia 1896. During World War I, a process to make phthaUc anhydride by the oxidation of naphthalene ia the vapor phase over a vanadium and molybdenum oxide catalyst was developed ia the United States (5). Essentially the same process was developed iadependendy ia Germany, with U.S. patents being granted ia 1930 and 1934 (6,7). 

Naphthalene (qv) from coal tar continued to be the feedstock of choice ia both the United States and Germany until the late 1950s, when a shortage of naphthalene coupled with the availabihty of xylenes from a burgeoning petrochemical industry forced many companies to use o-xylene [95-47-6] (8). Air oxidation of 90% pure o-xylene to phthaUc anhydride was commercialized ia 1946 (9,10). An advantage of o-xylene is the theoretical yield to phthaUc anhydride of 1.395 kg/kg. With naphthalene, two of the ten carbon atoms are lost to carbon oxide formation and at most a 1.157-kg/kg yield is possible. Although both are suitable feedstocks, o-xylene is overwhelmingly favored. Coal-tar naphthalene is used ia some cases, eg, where it is readily available from coke operations ia steel mills (see Steel). Naphthalene can be produced by hydrodealkylation of substituted naphthalenes from refinery operations (8), but no refinery-produced napthalene is used as feedstock. Alkyl naphthalenes can be converted directiy to phthaUc anhydride, but at low yields (11,12). 

Approximately 45% of the world s phthaUc anhydride production is by partial oxidation of 0-xylene or naphthalene ia tubular fixed-bed reactors. Approximately 15,000 tubes of 25-mm dia would be used ia a 31,000 t/yr reactor. Nitrate salts at 375—410°C are circulated from steam generators to maintain reaction temperatures. The resultant steam can be used for gas compression and distillation as one step ia reduciag process energy requirements (100). 

Another sulfur dioxide appHcation in oil refining is as a selective extraction solvent in the Edeleanu process (323), wherein aromatic components are extracted from a kerosene stream by sulfur dioxide, leaving a purified stream of saturated aHphatic hydrocarbons which are relatively insoluble in sulfur dioxide. Sulfur dioxide acts as a cocatalyst or catalyst modifier in certain processes for oxidation of o-xylene or naphthalene to phthaHc anhydride (324,325). 

In the older method, still used in some CIS and East European tar refineries, the naphthalene oil is cooled to ambient temperatures in pans, the residual oil is separated from the crystals, and the cmde drained naphthalene is macerated and centrifuged. The so-called whizzed naphthalene crystallizes at ca 72—76°C. This product is subjected to 35 MPa (350 atm) at 60—70°C for several minutes in a mechanical press. The lower melting layers of the crystals ate expressed as Hquid, giving a product crystallizing at 78—78.5°C (95.5—96.5% pure). This grade, satisfactory for oxidation to phthaHc anhydride, is referred to as hot-pressed or phthaHc-grade naphthalene. 

Naphthalene. Until the 1960s, the principal outlet for naphthalene was the production of phthaHc anhydride however, more recently, o-xylene has replaced naphthalene as the preferred feedstock (see Phthalic acids). Nevertheless, of the 201,000 t produced in 1994 in Japan, 73.2% was used for phthaHc anhydride production. The rest was consumed in dye stuffs manufacture and a wide variety of other uses. Naphthalene is also used to produce phthaHc anhydride in the United Kingdom, Belgium, and the C2ech RepubHc, and can be used by Koppers in the United States in time of o-xylene shortages. In Europe, the traditional uses for naphthalene have been for the manufacture of P-naphthol and for dye stuff intermediates (see Dyes and dye... 

Some primaries have articles devoted to them and their derivatives, ie, Benzoic ACID, Phenol, Salicylic acid, and Phthalic anhydride as a derivative of phthahc acid. The primary p-naphthol is discussed in Naphthalene derivatives. 

Phthalic anhydride. Naphthalene is oxidized by air to phthalic anhydride in a Bubbling flmdized reaclor. Even though the naphthalene feed is in liquid form, the reaction is highly exothermic. Temperature control is achieved by removing heat through vertical tubes in the bed to raise steam [Graham and Way, Chem. Eng. Prog., 58, 96 (Januaiy 1962)]. 

Toluene hydrodealkylation to benzene and methane Phthalic anhydride by air oxidation of naphthalene Trickle bed reactor for hydrodesulfurizatiou... 

Phtnalic anhydride is made by oxidation of naphthalene at temperatures of 340 to 380°C (644 to 716°F) controlled by heat exchangers immersed in the bed. At these temperatures the catalyst is stable and need not be regenerated. The excellence of temperature control was a major fac tor for the adoption of this process, but it was obsolesced by 1972. 

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